Fan Y,
Zheng H,
Labalme S,
Lin W.
*
The University of Chicago, USA
Molecular Engineering of Metal-Organic Layers for Sustainable Tandem and Synergistic
Photocatalysis.
J. Am. Chem. Soc. 2023;
145: 4158-4165
DOI:
10.1021/jacs.2c12599
Key words
photpcatalysis - metal-organic layer - cobalt catalyst - dehydrogenative amination
Significance
A metal organic layer (MOL) Hf–Ir composite was prepared from a photosensitizing Ir–BBA
complex and HfCl4 under solvothermal conditions. A cobaloxime unit was added to the resulting Hf–Ir
MOL with a pyridylpropionate (PPA) tether to give Hf–Ir–CoPPA. The Hf–Ir–CoPPA promoted
a dehydrogenative amination of cyclohexanones to give the corresponding N-alkyl anilines with photo irradiation by blue LED. The amination of a steroidal 3,17-diketone
took place with excellent chemoselectivity to give the corresponding A-ring amination
product exclusively.
Comment
ICP analysis of Hf–Ir–CoPPA revealed that the MOL composite had a Hf/Ir/Co ratio of
1.0/0.54/0.40. A 2D-monolayered double-decker structure of Hf–Ir–CoPPA was constructed
with Hf12 cluster units and bridging-ligand units Ir–BBA. Hf–Ir–CoPPA was recovered by centrifugation
and reused 8 times without significant loss of its catalytic performance. Hf–Ir–CoPPA
also catalyzed the Heck-type coupling of alkyl iodides with styrenes to give the corresponding
β-substituted styrenes.
